Process of manufacturing bromids from bromin-containing solutions.



'No. 733,467. PATENTED JULY 14, 1903.

H. H. 110W. Y

- PROCESS OF MANUFACTURING BROMIDS PROM BROMIN CONTAINING SOLUTIONS.

APPLICATION FILED MAY 21, 1903.

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A flu/(UM UNITED STATES Fatented July 14, 190s.

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HERBERT H. DOW, OF MIDLAND, MICHIGAN.

SPECIFICATION forming part of Letters Patent No. 733,467, dated July 14,1903.

Application filed May 21,1903- Serial No. 158,079. (No specimens.

To all whom it may concern-.-

Be it known that I, HERBERT H. Dow, a citizen of the United States, anda resident of Midland, county of Midland, and State of Michigan, haveinvented a new and useful Improvement in Processes of ManufacturingBromids from Bromin-Containing Solutions, of which the following is aspecification, the principle of the invention being herein explained andthe best mode in which I have contemplated applying that principle, soas to distinguish it from other inventions.

My invention consists in an improved process for manufacturing bromidsfrom bromincontaining solutions, such as natural brines or artificialsolutions of a bromid, and is especially adapted for the manufacture ofammonium bromid.

Said process consists of a series of steps hereinafter fully described.

The annexed drawing and the following description set forth in detailone mode of carrying out the invention, such disclosed meansconstituting but one of various ways in which the principle of theinvention may be used.

In said annexed drawing is represented a diagrammatic view of a form ofapparatus used in my improved process.

In said apparatus A represents a brine-reservoir in which the brine maybe oxidized in any of the ways explained in my United States LettersPatent, Reissue No. 11,232, with the formation of free bromin.

B represents a series of blowout towers similar to those described in myUnited States Letters Patent No. 714,160. 0 represents anabsorption-tower of similar construction, and D represents a rotaryexhauster or similar device for keeping the air in circulation.

It will be seen that the towers B, the airpipe 1), the tower C, theair-pipe c, the blower D, and the air-pipe d constitute an air-circuitsimilar to that described in above-mentioned Reissue Patent No. 11,232.No claim for novelty is therefore made to this part of the apparatus.

Connected with the absorption-tower O by the duct 0 and adapted toreceive material from such absorption-tower is the containin g vessel E,and connected with said containing vessel by the'duct f, also adapted todischarge material into said containing vessel E,

is-the containing vessel F. Material may be pumped from the container Eto the absorption-tower O by means of the pump e. Outlets are providedfor the waste brine or liquor from the towers B and for bromid from thecontainer E through the ducts b and 6, respectively.

If the absorption-tower 0 contained a fixed alkali and the apparatuscould be used as explained in above-mentioned patent, Reissue No.11,232, a bromid would result. If, however, the tower C was suppliedwith ammonium hydrate and the process was carried on as explained insaid patent, some ammonia would be blown out and would pass along thepipe 0 through the blower D and connecting-pipe d and would come intocontact with the bromin contained in the brine in the towers B. Thisammonia would here neutralize some of the bromin contained in thebrineaccording to the following formula:

8NH OH+ 6Br:6NH,Br-}-8H O+N and thus only a part of the bromin would becarried over by the air into the tower C, another part being neutralizedwith the formation of ammonium bromid, as explained, and passing outwith the brine waste at b; This process is therefore not an economicalmethod of making ammonium bromid, as both ammonia and bromin are wasted.

Bromin is very much more soluble in a bromid than it is in a chlorid,and, as explained in my-United States Letters Patent No. 711,160, anatural brine is constituted mainly of a solution of various chlorids.Now if the tower O is supplied with a solution of ammonium bromid andthe blower D is started and the air is caused to circulate, as indicatedby the arrows, the bromin-laden air will come in contact with theammonium bromid in the tower O, and the bromin will be absorbed with theproduction of a liquid of more or less orange color, this color beingdue to the presence of free bromin, as may be readily shown by testing alittle of the liquid with chloroform or carbon disulfid, in either ofwhich cases the bromin will be taken up by the added solvent and. theammoniumbromid solution rendered colorless. This bromin solution ofammonium bromid is allowed to pass out of the tower G into thecontaining vessel E. Here the free bromin is neutralized by a smallamount of ammonia solution admitted from the containing vessel F, andammonium bromid is formed according to the formula above given. Thissolution is again pumped over into the tower C by means of the pump 6and comes in contact with more bromin -laden air, is again charged withbromin, and the cycle repeated. It is thus seen that ammonium bromid maybe made from bromin-laden air without undue loss of either ammonia orbromin.

It will be apparent to any one versed in the subject of chemistry andacquainted with my United States Letters Patent No. 714,160 that themethods there outlined for purifying the bromin contained inbromin-laden air could also be applied to the process herein disclosed.It will also be evident that the brine escaping at b can be reworked forrecovering the free and combined bromin therein contained, as explainedin said patent. It will also be apparent that in order to operate theapparatus in the most successful manner the bromin-laden air should beas rich in bromin as possible, and to produce this result only a limitedamount of air should be passed through the brine. Under these circumstances the waste at b will always contain a considerable quantity offree bromin. This waste should therefore be used in a supplemental oradditional apparatus for the recovery of this material; but as suchapparatus is fully described and explained in Patent No. 714,160, abovereferred to, it is not necessary to again describe the process.

The production of air containing a very large amount of bromin of a highdegree of purity can be accomplished by using an artificial brominsolution for charging the air; but we do not consider this necessary ordesirable except when a product having maximum purity is desired.

While I particularly recommend this process for the manufacture ofbromid of ammonia, yet it is evident that any bromid can be formed inthe same manner.

Wherever the Word pure is used in the following claims it should beunderstood as meaning an article of sufficient purity to be a commercialproduct.

Other modes of applying the principle of my invention may be employedinstead of the one explained, change being made as regards the step orsteps herein disclosed, provided the means stated by any one of thefollowing claims or the equivalent of such stated means be employed.

I therefore particularly point out and distinctly claim as myinvention 1. The steps in the process of manufacturing a bromid frombromin-containing solutions which consist, in bringing air, first intocontact with a solution containing free bromin, and then into contactwith a pure bromid.

2. The steps in the process of manufacturing a bromid frombromin-containing solutions which consist, in bringing air, first intocontact with a solution containing free bromin, and then into contactwith pure ammonium bromid.

3. The steps in the process of manufacturing a bromid frombromin-containing solutions which consist, in bringing air, first intocontact with sodium-chlorid solution containing free bromin, and theninto contact with pure ammonium bromid.

4. The'steps in the process of manufacturing a bromid frombromin-containing solutions which consist, in absorbing bromin frombromin-laden air by means of a pure bromid, and then subsequently takingup the bromin thus absorbed by a suitable material that will combinechemically with bromin.

5. The steps in the process of manufacturing a bromid frombromin-containing solutions which consist, in absorbing bromin frombromin-laden air by means of pure ammonium bromid, and then subsequentlytaking up the bromin thus absorbed with ammonia.

6. The steps in the process of manufacturing a bromid frombromin-containing solutions which consist, in absorbing bromin frombromin-laden air by means of pure ammonium bromid, subsequently takingup the bromin thus absorbed by a suitable ammoniacontaining material,and then using the bromid so formed as a solvent for absorbingadditional quantities of bromin from bromin laden air.

7. The steps in the process of manufactur ing a bromid frombromin-containing solutions which consist, in absorbing bromin frombromin-laden air by means of pure ammonium bromid, subsequently takingup the bromin thus absorbed with ammonia, and then using the ammoniumbromid so formed as a solvent for absorbing additional quantities ofbromin from bromin-laden air. 1

8. The steps in the process of manufacturing a bromid frombromin-containing solu tions which consist, in oxidizing the solution,blowing out the bromin thus set free, absorbing the bromin by means of apure bromid,- and then taking up the bromin thus absorbed by a suitablematerial that will combine chemically with bromin.

9. The steps in the process of manufacturing a bromid frombromin-containing solubromid, taking up the bromin thu's absorbed thenblowing out, purifying, and absorbing with ammonia, and then using theammonium the bromin in a suitable ammonia-containing IO bromid so formedas a solvent for absorbing material.

additional quantities of bromin from bromin- Signed by me this 19th dayof May, 1903.

5 laden air. HERBERT H. DOW.

11. The steps in the process of manufactur- Attest: ing a bromid frombromin-containing solu- D. T. DAVIES,

tions which consist, in oxidizing the solution, G. W. SAYWELL.

